Automatic evaluation and data generation for analytical chemistry instrumental analysis exercises

In general, laboratory activities are costly in terms of time, space, and money. As such, the ability to provide realistically simulated laboratory data that enables students to practice data analysis techniques as a complementary activity would be expected to reduce these costs while opening up very interesting possibilities. In the present work, a novel methodology is presented for design of analytical chemistry instrumental analysis exercises that can be automatically personalized for each student and the results evaluated immediately. The proposed system provides each student with a different set of experimental data generated randomly while satisfying a set of constraints, rather than using data obtained from actual laboratory work. This allows the instructor to provide students with a set of practical problems to complement their regular laboratory work along with the corresponding feedback provided by the system's automatic evaluation process. To this end, the Goodle Grading Management System (GMS), an innovative web-based educational tool for automating the collection and assessment of practical exercises for engineering and scientific courses, was developed. The proposed methodology takes full advantage of the Goodle GMS fusion code architecture. The design of a particular exercise is provided ad hoc by the instructor and requires basic Matlab knowledge. The system has been employed with satisfactory results in several university courses. To demonstrate the automatic evaluation process, three exercises are presented in detail. The first exercise involves a linear regression analysis of data and the calculation of the quality parameters of an instrumental analysis method. The second and third exercises address two different comparison tests, a comparison test of the mean and a t-paired test.

PREDICTING THE BOILING POINT OF PCDD/Fs BY THE QSPR METHOD BASED ON THE MOLECULAR DISTANCE-EDGE VECTOR INDEX

The quantitative structure property relationship (QSPR) for the boiling point (Tb) of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was investigated. The molecular distance-edge vector (MDEV) index was used as the structural descriptor. The quantitative relationship between the MDEV index and Tb was modeled by using multivariate linear regression (MLR) and artificial neural network (ANN), respectively. Leave-one-out cross validation and external validation were carried out to assess the prediction performance of the models developed. For the MLR method, the prediction root mean square relative error (RMSRE) of leave-one-out cross validation and external validation was 1.77 and 1.23, respectively. For the ANN method, the prediction RMSRE of leave-one-out cross validation and external validation was 1.65 and 1.16, respectively. A quantitative relationship between the MDEV index and Tb of PCDD/Fs was demonstrated. Both MLR and ANN are practicable for modeling this relationship. The MLR model and ANN model developed can be used to predict the Tb of PCDD/Fs. Thus, the Tb of each PCDD/F was predicted by the developed models.

Evaluation of phenotypic stability of resistance to Phytophthora spp. in cacao clones

Resistance of fourteen Theobroma cacao clones to Phytophthora spp. was evaluated using stem inoculations on grafted seedlings. Concepts of phenotypic stability were used to interpret the results and to express horizontality of the resistance. The linear regression coefficient 'b', the determination coefficient (R²) and average lesion size were used to determine the level of horizontal resistance, the phenotypic stability and the predictability of all clones. The results indicated that clones P 7 and MA 15 present highest levels of horizontal resistance and stability, but with moderate predictability. Clones CAS 1 and CEPEC 13 were classified as those with high horizontal resistance, stability and predictability, while clones PA 30, UF 650 and SIAL 88 and EET 59 showed intermediate resistance and stability and high predictability. Clones SPA 17, OC 61, PA 150, SIAL 505, ICS 1 and R 41 presented high susceptibility and intermediate or low stability and moderate or high predictability.

Past, present and future - assessing changes in aquatic environments using subfossil diatoms

The deterioration of surface waters is one of the most important issues in the environmental management of the European Union. Thus, the EU Water Framework Directive 2000/60/EC (WFD) requires “good ecological and chemical status” of surface waters by 2015 allowing only a slight departure from ecological reference conditions characterized by the biological communities typical for the conditions of minimal anthropogenic impact. The WFD requires the determination of ecological reference conditions and the present ecological status of surface waters. To meet this legislative demand, sedimentary diatom assemblages were used in these studies with various methods 1) to assess natural and human activity induced environmental changes, 2) to characterize background conditions 3) to evaluate the present ecological status and 4) to predict the future of the water bodies in the light of palaeolimnological data. As the WFD refers to all surface waters, both coastal and inland sites were included. Two long and two short sediment cores from the Archipelago Sea in the northern Baltic Sea were examined for their siliceous microfossils in order to assess (1) the Holocene palaeoenvironmental history and (2) the recent eutrophication of the area. The diatom record was divided into local diatom assemblage zones (LDAZ, long cores) and diatom assemblage zones (DAZ, short cores). Locally weighted weighted averaging regression and calibration (LWWA) was applied for the quantitative reconstruction of past TN concentrations (short cores). An age model for the long cores was constructed by using independent palaeomagnetic and AMS-14C methods. The short cores were dated using radiometric (210Pb, 226Ra and 137Cs) methods. The long cores date back to the early history of the Archipelago Sea, which was freshwater – no salinity increase referable to the brackish phase of the Yoldia Sea is recognized. The nutrient status of the lacustrine phase was slightly higher in the Archipelago Sea than in the Baltic Proper. Initial brackish-water influence is observed at 8 150 ±80 cal. BP (LDAZ4), but fully brackish conditions were established at 7 700 ±80 cal. BP (LDAZ5). The diatom assemblages indicate increasing salinity, warming climate and possible eutrophic conditions during the lacustrine to brackish-water transition. The decreasing abundance of Pseudosolenia calcar-avis (Schultze) Sundström and the increasing abundance of the ice-cover indicator species Pauliella taeniata (Grunow) Round and Basson indicate decreasing salinity and climatic cooling after ca. 5 000 cal. BP. Signs of eutrophication are visible in the most recent diatom assemblage zones of both short cores. Diatom-inferred total nitrogen (DI-TN) reconstructions partially fail to trace the actual measured total nitrogen concentrations especially from the late 1980s to the mid 1990s. This is most likely due to the dominating diatom species Pauliella taeniata, Thalassiosira levanderi Van Goor and Fragilariopsis cylindrus (Grunow) W. Krieger being more influenced by factors such as the length of the ice-season rather than nutrient concentrations. It is concluded that the diatom assemblages of the study sites are principally governed by climate fluctuations, with a slight influence of eutrophication visible in the most recent sediments. There are indications that global warming, with reduced ice cover, could impact the spring blooming diatom species composition in the Archipelago Sea. In addition, increased sediment accumulation in the early 90s coincides with the short ice-seasons suggesting that warming climate with decreasing ice-cover may increase sedimentation in the study area. The diverse diatom assemblages dominated by benthic species (54 %) in DAZ1 in the Käldö Fjärd core can be taken as background diatom assemblages for the Archipelago Sea. Since then turbidity has increased and the diatom assemblages have been dominated by planktonic diatoms from around the mid 1800s onwards. The reconstructed reference conditions for the total nitrogen concentrations fluctuate around 400 μg l-1. Altogether two short sediment cores and eight short cores for top-bottom analysis were retrieved from Lake Orijärvi and Lake Määrjärvi to assess the impact of the acid mine drainage (AMD) derived metals from the Orijärvi mine tailings on the diatom communities of the lakes. The Cu (Pb, Zn) mine of Orijärvi (1757 – 1956) was the first one in Finland where flotation techniques (1911 – 1955) were used to enrich ore and large quantities of tailings were produced. The AMD derived metal impact to the lakes was found to be among the heaviest thus far recorded in Finland. Concentrations of Cu, Pb and Zn in Lake Orijärvi sediments are two to three orders of magnitude higher than background values. The metal inputs have affected Lake Orijärvi and Lake Määrjärvi diatom communities at the community levels through shifts in dominant taxa (both lakes) and at the individual level through alteration in frustule morphology (Lake Orijärvi). At present, lake water still has elevated heavy metal levels, indicating that the impact from the tailings area continues to affect both lakes. Lake Orijärvi diatom assemblages are completely dominated by benthic species and are lacking planktonic diatoms. In Lake Määrjärvi the proportion of benthic and tychoplanktonic diatoms has increased and the planktonic taxa have decreased in abundance. Achnanthidium minutissimum Kützing and Brachysira vitrea (Grun.) R. Ross in Hartley were the most tolerant species to increased metal concentrations. Planktonic diatoms are more sensitive to metal contamination than benthic taxa, especially species in the genus Cyclotella (Kützing) Brébisson. The ecological reference conditions assessed in this study for Lake Orijärvi and Lake Määrjärvi comprise diverse planktonic and benthic communitites typical of circumneutral oligotrophic lakes, where the planktonic diatoms belonging to genera Cyclotella , Aulacoseira Thwaites, Tabellaria Ehrenberg and Asterionella Hassall dominate in relative abundances up to ca. 70%. The benthic communities are more diverse than the planktonic consisting of diatoms belonging to the genera Achnanthes Bory, Fragilaria Lyngbye and Navicula St. Vincent. This study clearly demonstrates that palaeolimnological methods, especially diatom analysis, provide a powerful tool for the EU Water Frame Work Directive for defining reference conditions, natural variability and current status of surface waters. The top/bottom approach is a very useful tool in larger-scale studies needed for management purposes. This “before and after” type of sediment sampling method can provide a very time and cost effective assessment of ecological reference conditions of surface waters.

Determination of Alkalinity and dissociation constants of high salinity waters: use of F5BC titration function

Measurements of parameters expressed in terms of carbonic species such as Alkalinity and Acidity of saline waters do not analyze the influence of external parameters to the titration such as Total free and associated Carbonic Species Concentration, activity coefficient, ion pairing formation and Residual Liquid Junction Potential in pH measurements. This paper shows the development of F5BC titration function based on the titrations developed by Gran (1952) for the carbonate system of natural waters. For practical use, samples of saline waters from Pocinhos reservoir in Paraiba were submitted to titration and linear regression analysis. Results showed that F5BC involves F1x and F2x Gran functions determination, respectively, for Alkalinity and Acidity calculations without knowing "a priori" the endpoint of the titration. F5BC also allows the determination of the First and Second Apparent Dissociation Constant of the carbonate system of saline and high ionic strength waters.

Guava fruit loss caused by rust

The aim of this paper was to estimate the loss caused by rust (Puccinia psidii) to 'Paluma' guava production in orchards located in Rio de Janeiro State. The disease intensity on the reproductive organs of plants was observed during two chemical control experiments carried out in 2003 and 2004. The loss was estimated based on simple linear regression and the production reduction (fruit number and weight ha-1) on the incidence of diseased buds and fruits. In the first experiment, no relationship was established between incidence of diseased buds and loss since there was a delay in spraying and the incidence of buds showing rust was high (mean of 47%) at the beginning of flowering. In the second experiment (2003-2004), spraying occurred at the beginning of the epidemics and there was a linear relationship between incidence of diseased buds and loss, justifying fungicide intervention at this stage. For the fruiting stage, a significant relationship was found between incidence of diseased fruits and loss in both experiments. In the absence of chemical control, rust reduced fruit production by around 90%.

Problems and potentialities of e-Learning for regular undergraduate courses in emergency medicine

BACKGROUND: E-learning techniques are spreading at great speed in medicine, raising concerns about the impact of adopting them. Websites especially designed to host courses are becoming more common. There is a lack of evidence that these systems could enhance student knowledge acquisition. GOAL: To evaluate the impact of using dedicated-website tools over cognition of medical students exposed to a first-aid course. METHODS: Prospective study of 184 medical students exposed to a twenty-hour first-aid course. We generated a dedicated-website with several sections (lectures, additional reading material, video and multiple choice exercises). We constructed variables expressing the student's access to each section. The evaluation was composed of fifty multiple-choice tests, based on clinical problems. We used multiple linear regression to adjust for potential confounders. RESULTS: There was no association of website intensity of exposure and the outcome - beta-coeficient 0.27 (95%CI - 0.454 - 1.004). These findings were not altered after adjustment for potential confounders - 0.165 (95%CI -0.628 - 0.960). CONCLUSION: A dedicated website with passive and active capabilities for aiding in person learning had not shown association with a better outcome.

Osingonjakopolitiikan määräytyminen ja sen osakekurssivaikutukset Helsingin pörssissä

Tämän työn tarkoituksena oli tutkia lineaarisen regressioanalyysin avulla sekä osingonjakopolitiikan määräytymiseen vaikuttavia tekijöitä että osinkojen osakekurssivaikutusta Helsingin pörssissä. Osinkopolitiikan määräytymistä tutkittiin yhtiön koon, kannattavuuden, velkaisuuden, investointi- ja kasvumahdollisuuksien sekä sisäpiirin omistuksen avulla. Käytetty aineisto koostuu Helsingin pörssissä noteerattujen yhtiöiden tilinpäätösluvuista ja osakekurssitiedoista vuosina 2000-2010. Empiiriset tutkimukset osoittivat, että osinkotuottoon vaikuttavia tekijöitä Helsingin pörssissä ovat yhtiön kannattavuus, velkaisuus, investointi- ja kasvumahdollisuudet sekä sisäpiirin omistus. Saadut tulokset ovat samansuuntaisia aikaisempien tutkimusten kanssa. Toinen merkittävä löydös on, että osingoilla todettiin olevan positiivinen yhteys osakekurssimuutoksiin Helsingin pörssissä. Osinkojen ja osakekurssin välinen yhteys tukee signalointiteoriaa.

Asuntosijoittaminen: demografisten ja taloudellisten muuttujien vaikutus asuntojen hinta- ja vuokrakehitykseen Suomessa

Tutkielman tavoitteena on tehdä katsaus asuntosijoittamiseen sekä löytää asuntosijoittajalle tärkeää tietoa asuntojen hinta- ja vuokrakehitykseen vaikuttavista alueellisista tekijöistä. Asuntojen hintoihin vaikuttavia tekijöitä tutkitaan sekä kasvukaupungeissa että rakennemuutosalueilla. Asuntojen vuokrakehitykseen vaikuttavia selittäviä tekijöitä tutkitaan koko Suomen, pääkaupunkiseudun ja muun Suomen alueilla. Tutkimus toteutetaan käyttäen lineaarista regressioanalyysiä ja käytettävä aineisto koostuu muuttujien aikasarjoista vuosilta 1988–2010 sekä 1996–2009. Saatujen tulosten perusteella nettokansantulolla ja asuntokunnan käytet-tävissä olevalla rahatulolla on selkeä vaikutus asuntojen hintakehitykseen kasvukeskuksissa. Rakennemuutosalueilla työllisyyden ja teollisuuden vaikutukset ovat vahvoja. Asuntojen vuokriin vaikuttavista tekijöistä mm. asuinkerrostalokannalla, aloittaneiden yritysten määrällä ja asuntokunnan käytettävissä olevalla rahatulolla voidaan nähdä olevan selkeä vaikutus neliövuokran kehitykseen.

Spatio-temporal modelling of the duration of the cotton cycle in the State Of Goiás, Brazil

The objective of this work was to develop and validate a mathematical model to estimate the duration of cotton (Gossypium hirsutum L. r. latifolium hutch) cycle in the State of Goiás, Brazil, by applying the method of growing degree-days (GD), and considering, simultaneously, its time-space variation. The model was developed as a linear combination of elevation, latitude, longitude, and Fourier series of time variation. The model parameters were adjusted by using multiple-linear regression to the observed GD accumulated with air temperature in the range of 15°C to 40°C. The minimum and maximum temperature records used to calculate the GD were obtained from 21 meteorological stations, considering data varying from 8 to 20 years of observation. The coefficient of determination, resulting from the comparison between the estimated and calculated GD along the year was 0.84. Model validation was done by comparing estimated and measured crop cycle in the period from cotton germination to the stage when 90 percent of bolls were opened in commercial crop fields. Comparative results showed that the model performed very well, as indicated by the Pearson correlation coefficient of 0.90 and Willmott agreement index of 0.94, resulting in a performance index of 0.85.

Determination of the influence of the variation of reducing and non-reducing sugars on coffee quality with use of artificial neural network

The present study aimed at evaluating the use of Artificial Neural Network to correlate the values resulting from chemical analyses of samples of coffee with the values of their sensory analyses. The coffee samples used were from the Coffea arabica L., cultivars Acaiá do Cerrado, Topázio, Acaiá 474-19 and Bourbon, collected in the southern region of the state of Minas Gerais. The chemical analyses were carried out for reducing and non-reducing sugars. The quality of the beverage was evaluated by sensory analysis. The Artificial Neural Network method used values from chemical analyses as input variables and values from sensory analysis as output values. The multiple linear regression of sensory analysis values, according to the values from chemical analyses, presented a determination coefficient of 0.3106, while the Artificial Neural Network achieved a level of 80.00% of success in the classification of values from the sensory analysis.

Evaluation of empirical methods to estimate reference evapotranspiration in Uberaba, State of Minas Gerais, Brazil

Evapotranspiration is the process of water loss of vegetated soil due to evaporation and transpiration, and it may be estimated by various empirical methods. This study had the objective to carry out the evaluation of the performance of the following methods: Blaney-Criddle, Jensen-Haise, Linacre, Solar Radiation, Hargreaves-Samani, Makkink, Thornthwaite, Camargo, Priestley-Taylor and Original Penman in the estimation of the potential evapotranspiration when compared to the Penman-Monteith standard method (FAO56) to the climatic conditions of Uberaba, state of Minas Gerais, Brazil. A set of 21 years monthly data (1990 to 2010) was used, working with the climatic elements: temperature, relative humidity, wind speed and insolation. The empirical methods to estimate reference evapotranspiration were compared with the standard method using linear regression, simple statistical analysis, Willmott agreement index (d) and performance index (c). The methods Makkink and Camargo showed the best performance, with "c" values ​​of 0.75 and 0.66, respectively. The Hargreaves-Samani method presented a better linear relation with the standard method, with a correlation coefficient (r) of 0.88.

Validation study of an overall radiation balance estimation method under Ponta Grossa (PR) Brazil weather conditions

Radiation balance is the fraction of incident solar radiation upon earth surface which is available to be used in several natural processes, such as biological metabolism, water loss by vegetated surfaces, variation of temperature in farming systems and organic decomposition. The present study aimed to assess and validate the performance of two estimation models for Rn in Ponta Grossa city, Paraná State, Brazil. To this end, during the period of 04/01/2008 to 04/30/2011, from radiometric data collected by an automatic weather station set at the Experimental Station, of the State University of Ponta Grossa. We performed a linear regression study by confrontation between measurements made through radiometric balance and Rn estimates obtained from Brunt classical method, and the proposed method. Both models showed excellent performance and were confirmed by the statistical parameters applied. However, the alternative method has the advantage of requiring only global solar radiation values, temperature, and relative humidity.

The use of ALOS/PALSAR data for estimating sugarcane productivity

Some models have been developed using agrometeorological and remote sensing data to estimate agriculture production. However, it is expected that the use of SAR images can improve their performance. The main objective of this study was to estimate the sugarcane production using a multiple linear regression model which considers agronomic data and ALOS/PALSAR images obtained from 2007/08, 2008/09 and 2009/10 cropping seasons. The performance of models was evaluated by coefficient of determination, t-test, Willmott agreement index (d), random error and standard error. The model was able to explain 79%, 12% and 74% of the variation in the observed productions of the 2007/08, 2008/09 and 2009/10 cropping seasons, respectively. Performance of the model for the 2008/09 cropping season was poor because of the occurrence of a long period of drought in that season. When the three seasons were considered all together, the model explained 66% of the variation. Results showed that SAR-based yield prediction models can contribute and assist sugar mill technicians to improve such estimates.

Software for design of experiments and response modelling of cake ltration applications

Filtration is a widely used unit operation in chemical engineering. The huge variation in the properties of materials to be ltered makes the study of ltration a challenging task. One of the objectives of this thesis was to show that conventional ltration theories are di cult to use when the system to be modelled contains all of the stages and features that are present in a complete solid/liquid separation process. Furthermore, most of the ltration theories require experimental work to be performed in order to obtain critical parameters required by the theoretical models. Creating a good overall understanding of how the variables a ect the nal product in ltration is somewhat impossible on a purely theoretical basis. The complexity of solid/liquid separation processes require experimental work and when tests are needed, it is advisable to use experimental design techniques so that the goals can be achieved. The statistical design of experiments provides the necessary tools for recognising the e ects of variables. It also helps to perform experimental work more economically. Design of experiments is a prerequisite for creating empirical models that can describe how the measured response is related to the changes in the values of the variable. A software package was developed that provides a ltration practitioner with experimental designs and calculates the parameters for linear regression models, along with the graphical representation of the responses. The developed software consists of two software modules. These modules are LTDoE and LTRead. The LTDoE module is used to create experimental designs for di erent lter types. The lter types considered in the software are automatic vertical pressure lter, double-sided vertical pressure lter, horizontal membrane lter press, vacuum belt lter and ceramic capillary action disc lter. It is also possible to create experimental designs for those cases where the variables are totally user de ned, say for a customized ltration cycle or di erent piece of equipment. The LTRead-module is used to read the experimental data gathered from the experiments, to analyse the data and to create models for each of the measured responses. Introducing the structure of the software more in detail and showing some of the practical applications is the main part of this thesis. This approach to the study of cake ltration processes, as presented in this thesis, has been shown to have good practical value when making ltration tests.